EP0259734B1 - Siliconemulsion mit verbesserter Frost-/Auftaubeständigkeit - Google Patents

Siliconemulsion mit verbesserter Frost-/Auftaubeständigkeit Download PDF

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Publication number
EP0259734B1
EP0259734B1 EP87112639A EP87112639A EP0259734B1 EP 0259734 B1 EP0259734 B1 EP 0259734B1 EP 87112639 A EP87112639 A EP 87112639A EP 87112639 A EP87112639 A EP 87112639A EP 0259734 B1 EP0259734 B1 EP 0259734B1
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EP
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Prior art keywords
weight
parts
emulsion
freeze
nonoxynol
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Expired - Lifetime
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EP87112639A
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English (en)
French (fr)
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EP0259734A2 (de
EP0259734A3 (en
Inventor
Kathy Lynn Bakken
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Dow Silicones Corp
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Dow Corning Corp
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Publication of EP0259734A3 publication Critical patent/EP0259734A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Definitions

  • This invention relates to silicone emulsions useful as sealants which cure to an elastomer upon removal of water.
  • Silicone emulsions which are useful as sealants that cure to elastomers upon the removal of water are described in US-A-4,618,642.
  • nonionic surfactants can be used in the preparation of emulsions of silicone fluids.
  • a silicone caulking material based upon a silicone emulsion comprising an anionically stabilized, hydroxyl endblocked polydiorganosiloxane, dialkyltindicarboxylate, trifunctional silane, and inert, non-siliceous filler is improved by the addition of
  • This invention relates to a method of improving the freeze/thaw stability of an anionically stabilized silicone emulsion useful as a sealant comprising (A) 100 parts by weight of an anionically stabilized, hydroxyl endblocked polydiorganosiloxane having a weight average molecular weight of above 50,000, the organic radicals being monovalent hydrocarbon radicals containing less than 7 carbon atoms per radical and 2-(perfluoroalkyl)ethyl radicals having less than 7 carbon atoms per radical, present as an emulsion of dispersed particles in water, the emulsion having a pH of greater than 9 and a solids content of greater than 50 percent by weight, (B) from 0.075 to 0.75 part by weight of a dialkyltindicarboxylate, (C) from 0.2 to 5 parts by weight of a silane of the formula RSi(OR')3 where R is a monovalent hydrocarbon radical of from 1 to 4 carbon atoms inclusive and R' is a lower
  • Silicone emulsions useful as sealants and caulking materials have been produced by the addition of fillers and other additives to emulsions of anionically stabilized polydiorganosiloxane that have been compounded so that they cure to an elastomer upon the removal of water.
  • One of the preferred attributes of such a composition is the ability of the emulsion to resist freeze/thaw cycling. If the emulsion does not have this property, it is destroyed if the emulsion is allowed to freeze. Because it is very difficult to transport and store commercial materials throughout the country without exposing them to freezing conditions, it is a requirement that such commercial products be able to resist at least a number of freeze/thaw cycles.
  • ingredient (E), nonoxynol-10, a nonionic surfactant of the formula was unique in its ability to improve the number of freeze/thaw cycles an emulsion could be exposed to before the emulsion would fail. As little as 0.5 part by weight of this material added per 100 parts by weight of the polymer in the emulsion would show an improvement. The improvement got even better as the amount of nonoxynol-10 was increased up to 3 parts by weight. No higher amounts were tested since this gave freeze/thaw resistance that was more than that required.
  • Nonoxynol-10 is a commercial product available under the designation Makon® 10 from Stephan Chemicals. It has the formula shown above.
  • ingredient (F) ethylene glycol.
  • the ethylene glycol also aids in giving freeze/thaw stability. The freeze/thaw stability is improved as more ethylene glycol is used. With no nonoxynol-10, however, the ethylene glycol does not give sufficient freeze/thaw stability.
  • the amount of ethylene glycol used is from 0.5 to 6.0 parts by weight, with a preferred range of from 1 to 3 parts by weight.
  • the anionically stabilized, hydroxyl endblocked polydiorganosiloxane used in this invention is now well known in the art.
  • the hydroxyl endblocked polydiorganosiloxane (A) is one which can be emulsified, which imparts elastomeric properties to the product obtained after the removal of the water from the emulsion, and which is anionically stabilized.
  • Tensile strengths and elongations at break improve with increasing weight average molecular weight (Mw), with suitable tensile strengths and elongations obtained above 50,000 Mw.
  • the maximum weight average molecular weight is one which can be emulsified and which will give elastomeric properties to the product obtained after the water is removed from the emulsion.
  • Weight average molecular weights up to about 1,000,000 for the hydroxyl endblocked polydiorganosiloxane are expected to be practical for this invention.
  • the preferred Mw for the hydroxyl endblocked polydiorganosiloxanes are in the range of 200,000 to 700,000.
  • the organic radicals of the hydroxyl endblocked polydiorganosiloxane can be monovalent hydrocarbon radicals containing less than seven carbon atoms per radical and 2(perfluoroalkyl)ethyl radicals including 3,3,3-trifluoropropyl and 2-(perfluorobutyl)ethyl.
  • the hydroxyl endblocked polydiorganosiloxanes preferably contain organic radicals in which at least 50 percent are methyl.
  • the hydroxyl endblocked polydiorganosiloxanes are essentially linear polymers containing two organic groups per silicon atom but may include trace amounts of monoorganosiloxane or triorganosiloxy units present as impurities of the manufacturing process.
  • the preferred hydroxyl endblocked polydiorganosiloxanes are the hydroxyl endblocked polydimethylsiloxanes.
  • the preferred anionically stabilized, hydroxyl endblocked polydiorganosiloxanes are those prepared by the method of anionic emulsion polymerization described by Findlay et al. in U S-A-3,294,725, issued December 27, 1966, which shows the methods of polymerization, the ingredients used, and the hydroxyl endblocked polydiorganosiloxane obtained in an emulsion.
  • Another method of preparing the anionically stabilized, hydroxyl endblocked polydiorganosiloxane is described by Hyde et al. in US-A-2,891,920, issued June 23, 1958, which shows the hydroxyl endblocked polydiorganosiloxanes, the ingredients used, and their method of preparation.
  • hydroxyl endblocked polydiorganosiloxanes used in this invention are those which are anionically stabilized.
  • anionically stabilized means the hydroxyl endblocked polydiorganosiloxane is stabilized in emulsion with an anionic surfactant.
  • This silicone emulsion is in the form of an oil-in-water emulsion, i.e., the polydiorganosiloxane is a dispersed phase of particles in a continuous phase of water.
  • Ingredient (B) is a dialkyltindicarboxylate.
  • the dialkyltindicarboxylates are commercial materials.
  • Preferred dialkyltindicarboxylates include dibutyltindiacetate, dibutyltindilaurate, and dioctyltindilaurate with dioctyltindilaurate most preferred.
  • the dialkyltindicarboxylate can be used as is or it can be made into an emulsion.
  • a suitable emulsion is produced by emulsifying 50 percent by weight of the dialkyltindicarboxylate with water using about 10 percent by weight of sodium alkylarylpolyether sulfonate as the emulsifying agent in any of the well known methods of producing oil-in-water emulsions.
  • R can be a saturated hydrocarbon radical, such as methyl, ethyl, propyl, or butyl; or an unsaturated hydrocarbon radical such as vinyl.
  • Preferred R radicals are methyl and vinyl.
  • Preferred silanes are methyltrimethoxysilane, vinyltrimethoxysilane, and methyltri(ethylmethyloxime)silane.
  • Ingredient (D) is an inert, non-siliceous filler.
  • the filler is non-siliceous because the combination of ingredients (A) and (B) with a siliceous filler in an emulsion at a pH of greater than 9 will produce a reaction which appears to gradually crosslink the polymer, i.e., the modulus of the elastomer produced by drying the emulsion will gradually increase as the emulsion is aged. This is the effect which is greatly diminished by the composition of this invention.
  • Inert fillers suitable for use in anionic silicone emulsions are well known. The fillers have an average particle size below 10 micrometres, preferably below 2 micrometres.
  • fillers examples include carbon blacks, titanium dioxide, aluminum oxide, calcium carbonate, zinc oxide, mica, and various pigments. Titanium oxide has been found to be particularly useful as an ultraviolet light screening agent. Calcium carbonate is a preferred filler for the caulking materials of this invention, particularly when it has average particle size of less than 1 micrometre.
  • composition of this invention is based upon 100 parts by weight of polydiorganosiloxane in the emulsion of (A). From 0.075 to 0.75 part by weight of dialkyltindicarboxylate (B) is used to catalyze the cure of the composition. From 0.2 to 0.4 part by weight of the dialkyltindicarboxylate is preferred.
  • the amount of silane (C) can be varied from 0.2 to 5 parts by weight with a preferred range of from 0.4 to 2 parts by weight.
  • the amount of filler can vary from 50 to 200 parts by weight. The amount used is determined by the solids content of the emulsion of (A) and the nature of the filler or mixture of fillers chosen. Sufficient filler is used so that the final composition is of the required paste-type viscosity and has the characteristics described above which allow its use as a caulking material. If too little filler is used, the composition will not have a high enough viscosity. If too much filler is used, the material will be too stiff to extrude properly from the storage container, or the cured composition will be too brittle. If the ratio of filler to polydiorganosiloxane is too high, the cured product will not be elastomeric.
  • the preferred amount of the same filler is in the range of from 90 to 125 parts by weight per 100 parts by weight of polydimethylsiloxane.
  • the silicone compositions of this invention are prepared by ordinary high intensity mixing of the ingredients until a uniform material is obtained.
  • the emulsion of (A) is placed in the mixer, ingredients (B), (C), (E) and (F) are added and mixed, then the filler (D) is slowly added with mixing so that it is uniformly dispersed.
  • the order of addition of the ingredients does not appear to be critical. Because the final mixture is of a paste-type viscosity, the equipment must be strong enough to properly mix the ingredients at this viscosity. In the laboratory, a stainless steel container is used with a propeller-type, air-driven mixer. It is not desirable to build up heat during the mixing process. If necessary, the emulsion can be cooled before the filler is mixed in. After a uniform paste is obtained, the mixture is placed under vacuum or centrifuged to remove air entrapped during the mixing process. The deaired mixture is then placed into a sealed storage container.
  • Additional ingredients which can be added to the composition include such things as antifoams to aid during the mixing process, stabilizers such as organic amines, preferably 2-amino-2-methyl-1-propanol, and pigments such as titanium dioxide and carbon black to provide opaqueness or color to the cured caulking material.
  • stabilizers such as organic amines, preferably 2-amino-2-methyl-1-propanol
  • pigments such as titanium dioxide and carbon black to provide opaqueness or color to the cured caulking material.
  • the silicone composition of this invention is particularly useful as a caulking material. It can be easily extruded from a storage tube into place. Because it is an aqueous emulsion, it is easily tooled if necessary. Tools can be cleaned by washing with water. During cure of the emulsion, primarily water is given off so that there is no problem with odor. Because of the addition of the nonoxynol-10 of this invention, the emulsion can withstand repeated freezing and thawing during storage without destruction of the emulsion.
  • a series of silicone emulsions useful as caulking materials were prepared using different amounts of the nonionic surfactants nonoxynol-10 (falling under this invention) and nonoxynol-12 (falling outside of this invention) as additives to investigate their effect upon the freeze/thaw stability of the emulsion.
  • An emulsion was prepared by mixing in a container with an air driven propeller, 147 parts of an anionically emulsified polydimethylsiloxane emulsion having a solids content of about 70 percent by weight and a pH of about 10, the emulsion particles being less than 0.6 micrometres in average diameter and the polymer having a molecular weight average of greater than 240,000, 0.45 part of vinyltrimethoxysilane, the parts of nonoxynol-10 or nonoxynol-12 shown in Table I, 0.3 part of silicone antifoam having a solids content of about 25 percent by weight and a pH of about 3.5, 1.0 part of ethylene glycol, 0.3 part of polyacrylic acid filler dispersing agent, 0.3 part of hydrolyzed 2-methyl-3(2-aminoethylamino)propyl(methyl)dimethoxysilane, 4 part of titanium dioxide pigment, 2.5 parts of 2-amino-2-methyl-1-propanol, 0.5 part of 50
  • each sealant was then placed in a storage tube for test.
  • the tubes were frozen for 16 hours at -19°C, followed by 8 hours at room temperature to make one freeze/thaw cycle.
  • a 2.54 cm (one inch) bead of the sealant is then extruded from the tube and observed. Failure constitutes any change in appearance of the sealant emulsion.
  • compositions were prepared, varying the amount of nonoxynol-10 and ethylene glycol used to determine the effect upon freeze/thaw stability.
  • Each composition was similar to that of Example one, except the amounts of nonoxynol-10 and ethylene glycol were varied as shown in Table II, and the composition also contained 0.4 part of a methylcellulose thickener.
  • Each sealant was then tested for freeze/thaw stability with the results shown in Table II.
  • Example 2 A similar composition was prepared as in Example 1 except 2.0 parts of the 2-amino-2-methyl-1-propanol was used with 2.5 parts of a nonionic surfactant (Triton X-405®) of the formula used in place of the nonoxynol-10.
  • Triton X-405® a nonionic surfactant
  • Example 2 When used in a composition similar to that of Example 1, a freeze/thaw stabilizer of the formula commercial available as SURFYNOL® 485 from Air Products and Chemicals Inc., in place of the nonoxynol-10, failed after 1 cycle when used at levels of 0.5, 1.0, 1.5, and 2.0 parts.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Claims (8)

  1. Verfahren zum Verbessern der Stabilität einer anionisch stabilisierten Siliconemulsion beim Gefrieren und Wiederauftauen, die als Dichtungsmasse geeignet ist, enthaltend
    (A) 100 Gewichtsteile eines anionisch stabilisierten Polydiorganosiloxans mit blockierten, endständigen Hydroxylgruppen mit einem gewichtsmittleren Molekulargewicht über 50.000, wobei die organischen Reste einwertige Kohlenwasserstoffreste mit weniger als 7 Kohlenstoffatomen pro Rest und 2-(Perfluoralkyl)ethylresten mit weniger als 7 Kohlenstoffatomen pro Rest sind, anwesend als Emulsion in Wasser dispergierter Teilchen, wobei die Emulsion einen pH-Wert von größer 9 und einen Feststoffgehalt von größer als 50 Gew.-% aufweist,
    (B) von 0,075 bis 0,75 Gewichtsteile eines Dialkylzinndicarboxylats,
    (C) von 0,2 bis 5 Gewichtsteile eines Silans der Formel RSi(OR')₃, in der R ein einwertiger Kohlenwasserstoffrest mit 1 bis einschließlich 4 Kohlenstoffatomen ist und R' eine niedere Alkylgruppe mit 1 bis einschließlich 4 Kohlenstoffatomen oder ein Rest der Formel -N=CR₂ ist, in der R die zuvor angegebene Bedeutung hat,
    (D) von 50 bis 200 Gewichtsteile eines inerten nichtsilikatischen Füllstoffes,
    (E) mehr als 1 Gewichtsteil von Nonoxynol-10 und
    (F) von 0,5 bis 6,0 Gewichtsteile Ethylenglycol, um einer Zusammensetzung verbesserte Stabilität beim Gefrieren und Wiederauftauen zu verleihen.
  2. Verfahren nach Anspruch 1,
    dadurch gekennzeichnet,
    daß die Emulsion (A) einen Feststoffgehalt von größer als 70 Gew.-% aufweist, das Silan (C) Methyltrimethoxysilan ist und der Füllstoff (D) in einer Menge von 90 bis 125 Gewichtsteilen vorhanden ist.
  3. Verfahren nach Anspruch 1,
    dadurch gekennzeichnet,
    daß das Nonoxynol-10 in einer Menge von 1 bis 3 Gewichtsteilen vorhanden ist.
  4. Verfahren nach Anspruch 1,
    dadurch gekennzeichnet,
    daß das Ethylenglycol in einer Menge von 1 bis 3 Gewichtsteilen vorhanden ist.
  5. Verfahren nach Anspruch 2,
    dadurch gekennzeichnet,
    daß das Nonoxynol-10 (E) in einer Menge von 1 bis 3 Gewichtsteilen vorhanden ist und das Ethylenglycol (F) in einer Menge von 1 bis 3 Gewichtsteilen vorhanden ist.
  6. Zusammensetzung mit verbesserter Stabilität beim Gefrieren und Wiederauftauen, hergestellt nach dem Verfahren von Anspruch 1.
  7. Zusammensetzung mit verbesserter Stabilität beim Gefrieren und Wiederauftauen, hergestellt nach dem Verfahren von Anspruch 2.
  8. Zusammensetzung mit verbesserter Stabilität beim Gefrieren und Wiederauftauen, hergestellt nach dem Verfahren von Anspruch 5.
EP87112639A 1986-09-02 1987-08-29 Siliconemulsion mit verbesserter Frost-/Auftaubeständigkeit Expired - Lifetime EP0259734B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US902719 1986-09-02
US06/902,719 US4704422A (en) 1986-09-02 1986-09-02 Silicone emulsion having improved freeze/thaw resistance

Publications (3)

Publication Number Publication Date
EP0259734A2 EP0259734A2 (de) 1988-03-16
EP0259734A3 EP0259734A3 (en) 1990-02-14
EP0259734B1 true EP0259734B1 (de) 1992-04-01

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EP87112639A Expired - Lifetime EP0259734B1 (de) 1986-09-02 1987-08-29 Siliconemulsion mit verbesserter Frost-/Auftaubeständigkeit

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US (1) US4704422A (de)
EP (1) EP0259734B1 (de)
JP (1) JPH0689254B2 (de)
KR (1) KR960004360B1 (de)
AU (1) AU590962B2 (de)
CA (1) CA1313284C (de)
DE (1) DE3777922D1 (de)
ES (1) ES2008733A6 (de)

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FR2637606B1 (fr) * 1988-10-11 1990-12-14 Rhone Poulenc Chimie Dispersion aqueuse de silicone a base d'alcenyloxysilane reticulant en un elastomere par elimination de l'eau
US4892907A (en) * 1988-12-08 1990-01-09 General Electric Company Fast room temperature vulcanizing silicone elastomers
FR2666587B1 (fr) * 1990-09-10 1993-06-25 Dow Corning Sa Compositions de lubrifiant et leur utilisation.
EP0585330A1 (de) * 1991-05-02 1994-03-09 Consep Membranes, Inc. Oberflächen die durch insekten nicht bestiegen werden können oder auf denen sie sich nicht niederlassen können sowie verfahren und vorrichtung zu ihrer herstellung
AU1927492A (en) * 1992-04-30 1993-11-29 Envirosafe Solutions Corporation Aqueous dispersions stabilized from freeze/thaw cycles
US5482640A (en) * 1992-04-30 1996-01-09 Consep, Inc. Aqueous dispersions stabilized from freeze/thaw cycles
WO1993022395A1 (en) * 1992-04-30 1993-11-11 Envirosafe Solutions Corporation Aqueous dispersions stabilized from freeze/thaw cycles
DE4421500C1 (de) 1994-06-20 1995-12-07 Nuenchritz Chemie Gmbh Wäßrige, siliciumorganische Verbindungen enthaltende Zusammensetzungen
US5541253A (en) * 1994-10-11 1996-07-30 The B. F. Goodrich Company High solids copolymer dispersion from a latex and its use in sealants
US6040380A (en) * 1994-10-11 2000-03-21 Tremco Incorporated High solids copolymer dispersion from a latex and its use in caulks, sealants and adhesives
US5674937A (en) * 1995-04-27 1997-10-07 Dow Corning Corporation Elastomers from silicone emulsions having self-catalytic crosslinkers
US5753742A (en) * 1996-07-31 1998-05-19 The B.F.Goodrich Company High-solids, aqueous, polymeric dispersions
US5844007A (en) * 1996-10-21 1998-12-01 No Touch North America Lustering and protecting agent for rubber, vinyl, and the like
JP5089203B2 (ja) 2006-05-26 2012-12-05 株式会社リコー 用紙搬送装置、画像形成装置及びインクジェット記録装置
JP2009196803A (ja) 2008-02-25 2009-09-03 Konica Minolta Business Technologies Inc 用紙搬送装置
CN112805360A (zh) 2018-10-29 2021-05-14 陶氏环球技术有限责任公司 含有聚硅氧的织物护理组合物

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US4618642A (en) * 1985-05-02 1986-10-21 Dow Corning Corporation Silicone water-based caulking material

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Publication number Publication date
KR960004360B1 (ko) 1996-04-02
CA1313284C (en) 1993-01-26
DE3777922D1 (de) 1992-05-07
EP0259734A2 (de) 1988-03-16
AU7774387A (en) 1988-03-10
EP0259734A3 (en) 1990-02-14
JPS6368666A (ja) 1988-03-28
JPH0689254B2 (ja) 1994-11-09
AU590962B2 (en) 1989-11-23
ES2008733A6 (es) 1989-08-01
KR880004043A (ko) 1988-06-01
US4704422A (en) 1987-11-03

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